Manufacture of strongly basic azo-dyestuffs



Patented Nov. 15, 1932 UNITED, STATES PATENT OFFICE ACHILLE CQNZETTI, OF BASEL, SWITZERLAND; 'ASSIGNOR TO THE FIRM}: J.

S. .A., OE BASEL, SWITZERLAND' MANUFACTURE or s'rnonanr BAsIc Azo-nYEs'rUrrs I 7 No Drawing. Application filed July as, 1928, Serial No. 296,102, and in Germany August G, 1927 The present invention relates-to the manufacture of strongly basic monoazo-dyestufis and consists in converting nitrated primary and secondary amines of the benzene series by successive treatment with chloracetyl-chlm ride and a body of the pyridine group, into a basic body containing the group 11-NA-oo.on,.N

basic dyestuffs, that is to say they dye cotton with a tannin mordant intense and fast tints. As compared with the known strongly basic azo-dyestufl's which contain the strongly basic group as a quaternary nitrogen attached either. directly or through the GH -group to the benzene ring, the dyestuffs of this invention are characterized by containing th group NH.CO.CH as a bridge.

- Since each free amino-group can be converted into this strongly basic group by smooth reaction there is the possibility of obs taining a very large number of new combinations, especially also by introducingseveral such strongly basic groups into the dyestufi molecule.

By suitablechoice of a dyestuff which is fast to light and contains free amino-groups and is not useful in dyeing, there may be obtained by the process of thisinventiondyestuffs which dye with a tannin-mordant and yield on cotton tints of high fastness to light,

complete fastness to Washing, completetastyielding pure on weighted silk tints which are quite fast to washing and yield pure white discharges. Similarly, good dyeings' may be produced on leatherand jute. i

Example 1.13.8 kilos of para nitraniline Also dyestuffs can be obtained which yield are dissolved at C. in litres of toluene all the hydrochloric acid isexpelled and on, cooling the chloracetyl-para-nitranh line'separates completely inthe form of pale yellow hard crystals almost insoluble in' boiling water and melting at 182 C.

at; The chloracetyl-derivative isfjdissolved in -1001litresv-of pyridine andthe solution is gradually heated, whereby the masssolidi fies to a thickishcrystalniass owing to separationof the productof reactionand heatvis evolved, The whole is heated for a short time to'boiling and then cooled, whereby the 'pyrido-acetyl-para-nitraniline is completely separated in crystalline form. The product may be obtained pure by crystallization from boiling water in the form'of long white nee-' dles which melt at 267 C; It is very sparinglyv soluble in cold water. v

flhe pyridination may be procured more advantageously by 1 heating the t chloracetyla .pa-ra-nitraniline in 70, litres of water +7.9

formed; On cooling there is formed a magr; l

ma of large crystals which are-the hydrochloride of pyrioacetyl-para-nitraniline.

By reduction with iron and acetic acid in known manner there is obtaineds moothly an aqueous solution of pyridoacetyl-para-phenylene-diamine of the probable formula:

of caustic soda lye of 30 per cent strength,

and the whole is then heated to 40 C.

The dyestuff. is completely precipitated; it is filtered and dried. It is fully soluble in Water, dyes tannin-mordanted cotton pure v yellow and weighted silk a yellow which is fast to washing and very fast to light.

Example Q.The diazo-solution obtained in known manner from 7 .15 kilos of alphanaphthylamine is neutralized by means of sodium acetate and is run into a solution of 16 '3 kilos of N pyridoac-etyl-2z7-aminonaphthol of the formula: v

in 400 litres of water containing 7 kilos of crystallized sodium acetate, which solution was prepared hot but cooled before the coupling operation.

The dyestuii dyestannin-mordanted cotton pure blue-red and its dyeingson :weighted silk arefast to washing and very fast to light.

The N -pyridoacetyl-2 7 -aminonaphthol is made by chloracetylating 2:7-aminonaphthol in aqueous solution and heating the chloracetyl-2 i'7-aminonaphthol having the formula i nom-nnooomoi in pyridine or preferably in aqueous suspension with pyridine. There is thus obtained 'N-pyridoacetyl-2:7-aminonaphtho1 in the form-of hard, coarse, light-yellow crystals.

The dyestu'if obtained with alpha-naphthylamine hasthe following formula:

The product is almost insoluble in cold Water but easily soluble in hot water. The

solution in caustic soda lye is deep yellow.

Earample 3.16.6 kilos of ethyl-para-nitraniline are dissolved in 25 kilos of toluene at the temperature of the Water-bath; while stirring well 12.5 kilos of chloracetylchloride are dropped into the solution and the latter is stirred for 2 hours at 115 C. the separated crystalline chloracetyl-ethylpara-nitraniline, which is formed in good yield, is filtered. It melts at 14414:6 C. and probably has the formula:

CLCMM ONOZ This nitro-derivative is heated for a short time in pyridine or preferably in aqueous suspension with pyridine, whereby there is obtained in quantitative yield the pyridoacetyl-ethyl-para-nitraniline of melting point 216 C. and of the probable formula: I

From this latter compound by reduction by means of iron'and acetic acid there isobtained in good yield the pyridoacetyl-ethylpara-phenylenediamine.

The reduction liquor containing 29.15 kilos of this substituted para-phenylenediamine is diazotized by means of 30 kilos of concentrated hydrochloric acid and 6.9 kilos of sodium nitrite. The mineral acid is neutralized by means of sodium acetate and more crystallized sodium acetate amounting to 15 kilos is added, Into this diazo-solution is run 14. 1 kilos After cooling,

of beta-naphthol in 200 litres of water and 13 I kilos of fcaustic soda lye of 30 -,per cent;

strength.

The dyestuff thus produced is very easily soluble and dyes tannin-mordanted cotton an orange fast to washing and light and weight ed silk a yellow orange which yields awhite discharge andis; of good fastness to light.

' ,Ewample 4..- 10.7' kilos of para-nitrodiphenylamine are heated in 50 litres of toluene to 80C. To this mixture, while stirring well, 6.5 kilos of chloracetyl chloride are added by 'drops' and heating. is continued for 2 hours at 115 C. until all hydrochloric acid has been dispelled. After cooling, the beautiful crystalline chloracetyl-para-nitrodiphenylamine is filtered. Its melting point is 114.-'-115 C. and its probable formula;

H O-NOZ. e0 p 7 6H2 ('11 V This nitro-derivative is heatedfor a short time in pyridine or preferably in aqueous suspension with pyridine, whereby there are obtained in excellent yield pure white, lustrous crystals of pyridoacetyl-para-nitrodiphenylamine of melting point 203-204 C. and of the probable formula:

By the known method of reduction by means of iron and acetic acid there "is obtained from this compound the pyridoacetylpara-aminodiphenylamine.

A solution of this last-named base containing 34 kilos is diazotized by means of kilos of concentrated hydrochloric acid and 6.9 kilos of sodium nitrite. The mineral acid isneutralized by means of sodium acetate and more crystallized sodium acetate is added to the amount of 15 kilos. Into this diazo-solution is then run a solution of 14A kilos of beta-naphthol in 200 litres of water and 6.5 kilos of caustic soda lye of 30 per cent. strength. I

The dyestufl' thus produced is soluble in water and dyes tannin-mordanted cotton orange-red tints fast to washing and light. It dyes weighted silk red-orange which yields a white discharge and is satisfactorily fast to light. o

Further examples of dyestuffs obtainable in accordance with this invention:

body of the pyridine group into a-basic body containing the group R' NA .C0.OHz.N

wherein R represents an arylradical of the benzene andnaphthalene series and A'jrepresents hydrogen, alkyl or aryl of the benzene series, reducing the nitro group of the body 4 thus obtained; diazotizing and coupling same with an azo coupling' component of the benzene and naphthalene series and phenyL lmeth'ylpyrazolone. V v

QQ A process for the manufacture of strongly basic 'monoazo dyestufls consisting in converting a diazotizable compound of the benzene and naphthalene series by'successive treatment with chloracetyl-chloride andpyridine' into'a basic bodyfcontaining'the group wherein R represents an aryl radical of the benzene and naphthalene series and A repre-- V 1. A process for the manufacture of strongly basic monoazo-dyestufl's, consisting in converting nitrated primary and secondary amines of the benzene series by successive treatment with chloracetyl-chloride and a Solution in water Solution in con- Dyeing on tan- Dyestufi from g zg g the +sodium acetate centrated sul nin-mordanted y +acetic acid phuricacid cotton Pyridoacetyl-para-phenylenediamineacetoacetic-anilide..- Greensh yellow Green-yellow o Green-yellow Greenish-yellow pow er.

Pyridoacetyl-chloro-para-phenylenediamine beta-naphthol- Orange-red powder Orange-red Blue-red Red Pyridoacetyl chloro-para phenylenediamine-aphenyl Orange powder 7 Pure yellow Yellow Yellow CHg-pyrazolone. i I v Pyridoacetyl-meta-ainino-ortho-anisidinebeta-naphthol Light red powder Scarlet red Red-violet Blue-red Pyridoacetyl meta amino ortl1o anisidlnedi chloro Orangered powder Orange-yellow Red-brown Orange-yellow phenyl-CHrpyrazo1one i r I V PyrldoacetyllA-naphthylenediamine-ebeta-naphthol. Dark violet powder Dark red Blue Dark red Pyridoacetgl}; 0]rth0 nethoxy para phenylenediaminH Light red powder Scarlet-red Blue-red Red beta-nap t o V V Pyridoacletyl ortho amino para to1uidine phenyl CH; Oigmge-yellow pow- Orange-yellow Yellow Orange-yellow pyrazo one. er V Pyridoacetyl para pheny1enediamine pyrid0acetyl 2:7 Brownish red pow- Orange-red Ruby-red Red aminonaphthol. der a v i Para-toluldine pyridoacetyl-Z:T-annnonaphthoL. Red powder Orange-red V Blue-red Red-orange Amline)pyridoacetyl-2:7-aminonaphtnoli Light red powder Orange-red Blue-red Red-orange v v Para-toluidinHpyridoacetyl-lztaminonapht Red powder Blue-red Blue-red Blue-red Aniline-apyridoacetyl-l:4-amil1onaphth0l--- Blue-red powder Ruby-red Bluish-red Bluisli-red Dirlpelthyl-acetyl-amino-para-phenylenediamineabet Brown-red powder Scarlet-red Blue-red Red Pyridoacetyl ethyl paramethyl meta phenylenedi- Brick-red powder Orange Blue-red Orange amine-ebetanaphthol. Cl v l N.C0.0H:.N 52H:

What I claim is in treating mononitranilines with chlor- I acetyl-chloride, then treating the body thus obtained with pyridine and with a reducing agent capable of reducing the nitro group to the amino group, diazotizing the product thus obtained and coupling samewith an azo (;'0u )li'ng component of thebnzeneflndndplb thalene series and phenylmethylpyrazolone. i

4:. The strongly basic monoazo-dyestuifs obtained as 'herein beforedescribed and hav- I ing the followinglgeneml formula:

.v r 01 H :v vherein A fepresents hydidgen', alkyl or al yl of the benzene series andX an azo coupling 1 component of the benzene and naphthalene series or phenylmethylpyrazolone, said 2120'- dyestufis being in form of their hydro-chlorides more or less easily soluble in Waterand having the -properties of basicfdyestufl's dyeing tennin-mordanted textiles intense and fast tints, e

In witness whereof I'have hereunto signed my name this 16th day of July 1928.

Y ACHILLE CONZETTI.

so i 

